Process for altering fragrance with 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanone or 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butanone

ABSTRACT

Methods for preparing foodstuffs, flavoring compositions for foodstuffs, perfume compositions and ingredients for perfume compositions by including therein 4-(2,6,6-trimethyl-1-1,3cyclohexadien-1-yl)-2-butanone or 4-(6,6-dimethyl-2-methylene-3cyclohexen-1-yl)-2-butanone to produce: A. In food flavorings, raspberry, waxey, tobacco, rosey, ionone flavor notes or combinations of these and woody, tobacco, floral aroma notes for improving the taste and aroma of artificial strawberry, or other red berry (e.g. raspberry) flavoring compositions; and B. In perfumes, a sweet, fruity, woody, berry &#39;&#39;&#39;&#39;mimosa&#39;&#39;&#39;&#39; character as well as the foodstuff flavoring compositions and perfume compositions containing 4-(2,6,6-trimethyl-1,3cyclohexadien-1-yl)-2-butanone and/or 4-(6,6-dimethyl-2methylene-3-cyclohex-1-yl)-2-butanone.

United States Patent [191 Mookherjee et a].

[ Mar. 18, 1975 PROCESS FOR ALTERING FRAGRANCE WITH4-(2,6,6-TRIMETHYL-1,3- CYCLQHEXADIEN-1-YL)-2-BUTANONE oR4-(6,6-DIMETHYL-2-METHYLENE-3- CYCLOHEXEN-l-YL)-2-BUTANONE [75]Inventors: Braja Dulal Mookherjee, Matawan; Robert Walter Trenkle,Bricktown; Manfred Hugo Vock, West Orange, all of N.J.; Edward J.Shuster, Brooklyn, NY.

[73] Assignee: International Flavors & Fragrances Inc., New York, NY.

[22] Filed: Aug. 7, I973 [21] Appl. No.:'386,320

[52] US. Cl. 252/522 [51] Int. Cl ..C1lb 9/00 [58] Field of Search252/522 [56] References Cited UNITED STATES PATENTS 3,117,982 1/1964Barton 252/522 3,679,754 7/1972 Beereboom 252/522 Primary ExaminerSamRosen Attorney, Agent, or FirmArthur L. Liberman, Esq.; Harold Haidt,Esq.

[57] ABSTRACT Methods for preparing foodstuffs, flavoring compositionsfor foodstuffs, perfume compositions and ingredients for perfumecompositions by including therein 4-(2,6,6-trimethyl- 1- l,3-cyclohexadien-l-yl)-2- butanone or 4-(6,6-dimethyl-2-methylene-3-cyclohexen-l-yl)-2-butanone to produce:

a. In food flavorings, raspberry, waxey, tobacco, rosey, ionone flavornotes or combinations of these and woody, tobacco, floral aroma notesfor improving the taste and aroma of artificial strawberry, or other redberry (e.g. raspberry) flavoring compositions; and

b. In perfumes, a sweet, fruity, woody, berry mimosa character as wellas the foodstuff flavoring compositions and perfume compositionscontaining 4-(2,6,6-trimethyl-1,3-cyclohexadien-l-yl)-2- butanone and/or4-(6,6-dimethyl-2-methylene-3-cyclohex-1-yl)-2- butanone.

2 Claims, No Drawings PATENTEDKAR I 81915 3.872.031

3 30 0.8 .9 .E 70 -0.7 ,5 so 055 g 50 -05 5 4O F/C Atomic ratio 0.4 2 gHRate of inglfsase in weight E 10 -0.1

0 bi'z'sz'siom'z Amount of HF based on fluorine PROCESS FORALTERINGFRAGRANCEWITH 4-(2,6,6-TRIMETHYL-IJ-CYCLOHEXADIEN- lYL)-2-BUTANONE R4-(6,6-DIMETHYL-2-METHYLENE-3- CYCLOHEXEN-l-YL)-2-BUTANONE BACKGROUND OFTHE INVENTION The present invention relates to novel methods andcompositions using 4-(2,6,6-trimethyl-1,3-cyclohexadien-l-yl)-2-butanone and/or 4-(6,6-dimethyl-2-methylene-3-cyclohexen-l-yl)-2-butanone to alter the flavorand/or aroma of consumable materials.

There has been considerable work performed relating to substances whichcan be used to impart (or enhance) flavors to (or in) various consumablematerials, These substances are used to diminish natural materials someof which may be in short supply and to provide more uniform propertiesin finished products. Raspberry. waxey, tobacco, rosey, ionone flavornotes and woody, tobacco, floral aroma notes are particularly desirablefor many uses in fruit flavoring compositions and consumable articles,e.g., foodstuffs. Sweet, fruity, woody, berry mimosa" aromas areparticularly desirable in perfume compositions.

The flavor and fragrance material having the strucis disclosed inBritish Pat. No. 1,305,621 issued on Feb. 7, 1973.

4-( 2,6,6-trimethyl-l ,3-cyclohexadienl -yl)-2- butanone, having thestructure:

may be synthesized according to the technique of Wolf and Zink, Volume56, Helvetica Chimica Acta., Fasc 3 (1973) pp. 1,062-1,066, or accordingto Examples 1 and II of Rowland, US. Pat. No. 3,436,421 issued on April1, 1969 by means of bromination of a-dihydroionone followed bydebromination. 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butanone having the is also produced inthis process as a bi-product thereof [B.P. 65 C at 0.15 mm Hg.pressure]. 4-(2,6,6-

trimethyl-l,3-cyclohexadien-1-yl)-2-butanone is alsoshown to be abi-product in the cyclization of ill ionone to beta ionone by Kruk andDe Boer in Volume 87 Recueil (1968) pp. 641-654 as an intermediate inprepar' ing other perfumery compounds. The compound having thestructure:

is disclosed in Japanese Pat. No. 7,121,015 (Sak an and lsoe) issuedJune 14, 1971.

THE INVENTION wherein one of the dashed lines represents a carboncarbondouble bond, and the other dashed line represents a carbon-carbon singlebond. Thus, the 4-(2,6,6- trimethyl-l,3-cyclohexadien-l-yl)-2-butanoneand/or 4-(6,6-dimethyl-2-methylene-3-cyclohexen-l-yl)-2- butanone of ourinvention are capable of supplying and/or potentiating certain flavorand aroma notes usually lacking in many red-berry type flavors as wellas notes usually lacking in many perfumery materials, e.g., mimosa"aromas.

When the 4-(2,6,6-trimethyl-l,3-cyclohexadien-lyl)-2-butanone and/or4-(6,6-dimethyl-2-methylene-3- cyclohex-l-yl)-2-butanone of ourinvention is used as a food flavor adjuvant, the nature of theco-ingredients included with the said 4-(2,6,6-trimethyl-l,3-cyclohexadien-1-yl)-2-butanone and/or 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butan0ne in formulating theproductcomposition will also serve to alter the organolepticcharacteristics of the ultimate foodstuffs treated therewith. As usedherein in regard to flavors, the term alter in its various forms meanssupplying or imparting flavor character or note to otherwise bland,relatively tasteless substance or augmenting the existing flavorcharacteristic where a natural flavor is deficient in some regard orsupplementing the existing flavor impression to modify its quality,character or taste." As used herein, the term foodstuff includes bothsolid and liquid ingestible materials which usually do but need not havenutritional value. Thus, foodstuffs include meats, gravies, soups,convenience foods, beverages, dairy products, candies, vegetables,

'cereals, soft drinks, snacks and the like.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use being extensivelydescribed in the relevant literature. Apart from the requirement thatany such material be ingestibly" acceptable and thus non-toxic orotherwise non-deleterious nothing particularly critical resides inselection thereof. Accordingly, such materials which may in general becharacterized as flavoring adjuvants or vehicles comprise broadlystabilizers, thickeners, surface active agents, conditioners, otherflavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride,antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2 and 3 tertiary'butyl-4-hydroxyanisole), butylated hydroxy toluene(2,6-di-tertiary-butyl-4- methyl phenol), propyl gallate and the like,and sequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agaragar;carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatine, proteinaceous materials; lipids;carbohydrates; starches pectins, and elumsifiers, e.g., mono-anddiglycerides of fatty acids, skim milk mild powder, hexoses, pentoses,disaccharides, e.g., sucrose, corn syrup solids and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono-and diglycerides of fatty acids, lecithin, defoaming andflavordispersing agents such as sorbitan monostearate, potassiumstearate, hydrogentated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modi fiers such as peracetic acid, sodium chlorite, sodiumhyprochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, turmeric and curcuminand thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phsophate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acid, e.g.,fatty saturated acids, unsaturated acids and amino acids; alcohols,e.g., primary and secondary alcohols; esters; carbonyl compounds, e.g.,aldehydes and ketones as well as lactones; cyclic organic materialsincluding benzene derivatives; isocyclics, heterocyclics such as furansparticularly 2,5-dimethyl-3-acetyl furan and 2-methyl-2,3-dihydrofuran-3-one, puridines, pyrazines (particularly monoalkyl, dialkyl,trialkyl and tetraalkyl substituted pyrazines) and the like,sulfurcontaining materials including thiazoles, disulfides, thiols,sulfides, aldehydes, (for example, 3-phenyl-4- pentenal,3-phenyl-3-pentenal, S-phenyl-Z-pentenal, 2-phenyl-2-pentenal and2-phenyl-3-methyl-2- butenal); disulfides and the like; other flavorpotentiators such as monosodium glutamate, guanylates, inosinates,natural and synthetic flavorants such as vanillin, ethyl vanillin,diacetyl, phenethyl-2-furoate, maltol, natural gums and the like;spices, herbs, essential oils The specific flavoring adjuvant selectedfor use may I be either solid or liquid depending upon the desiredphysical form of the ultimate product, i.e., foodstuff, whethersimulated or natural, and should, in any event, be capable of providingan environment in which the 4-( 2,6,6-trimethyll ,3-cyclohexadien- I-yl)-2-butanone and/or4-(6,6-dimethyl-2-methylene-3-cyclohexen-lyl)-2-butanone can bedispersed or admixed to provide a homogeneous medium. In addition,selection of one or more flavoring adjuvants as well as the quantitiesthereof will depend upon the precise organoleptic character desired inthe finished product. Thus, in the case of flavoring compositions,ingredient selection will vary in accordance with the foodstuff to whichthe flavor and aroma are to be imparted. In contradistinction, in thepreparation of solid products, e.g., simulated foodstuffs, ingredientscapable of providing normally solid compositions should be selected suchas various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount of4-(2,6,6-trimethyl-l,3-cyclohexadien-l-yl)- 2-butanone and/or4-(6,6-dimethyl-2-methylene-3- cyclohexen-l-yl)-2-butanone employed in aparticular instance can vary over a relatively wide range whereby to itsdesired organoleptic effects having reference to the nature of theproduct are achieved. All parts and percentages given herein are byweight unless otherwise specified. Thus, correspondingly greater amountswould be necessary in those instances wherein the ultimate foodcomposition to be flavored is relatively bland to the taste, whereasrelatively minor quantities may suffice for'purposes of enhancing thecomposition merely deficient in natural flavor or aroma. Thus, theprimary requirement is that the amount selected to be effective, i.e.,sufficient to alter the organoleptic characteristics of the parentcomposition, whether foodstuff per se or flavoring composition. Thus,the use of insufficient quantities of 4-( 2,6,6-trimethyl-l ,3-cyclohexadien-1-yl)-2-butanone and/or 4-(6,6-dimethyl-2-methylene-3-cyclohexen-l-yl)-2-butanone will, of course,substantially vitiate any possibility of obtaining the desired resultswhile excess quantities prove needlessly costly and in extreme cases,may disrupt the flavoring aroma balance, thus proving selfdefeating.Accordingly, the terminology effective amount and sufficient amount isto be accorded a significance in the context of the present inventionconsistent with the obtention of desired flavoring effects.

Thus and with respect to ultimate food compositions, it has been foundthat quantities of 4-(2,6,6-trimethyll,3-cyclohexadien-lyl)-2-butanoneand/or 4-(6,6- dimethyl-2-methylene-3-cyclohex-l-yl)-2-butanone rangingfrom a small but effective amount, e.g., 0.02 parts per million up toabout 50 parts per million by weight based on total composition aresuitable. Concentrations in excess of the maximum quantity stated arenot normally recommended since they fail to provide commensurateenhancement of organoleptic properties. ln those cases wherein the4-(2,6,6- trimethyl-l,3-cyclohexadien-l-yl)-2-butanone and/or4-(6,6-dimethyl-2-methylene-3-cyclohexen-l-yl)-2- butanone is added tothe foodstuff as an integral component of the flavoring composition, itis, of course, eseential that the total quantity of flavoringcomposition employed be sufficient to yield an effective 4-(2,6,6-trimethyl-l,3-cyclohexadien-l-yl)-2-butanone 5 and/or4-(6,6'dimethyl-2-methylene-3-cycloliexen lyl)-2-butanone concentrationin the foodstuff product. Food flavoring compositions prepared inaccordance with the present invention preferably contain 4-(2,6,6-trimethyll,3-cyclohexadien-l-yl)'2-butanone and/or4-(6,6-dimethyI-Z-methylene-3-cyclohexen-l-yl)-2- butanone inconcentrations ranging from about 0.2% up to about 10% by weight basedon a total weight of said flavoring composition.

The compositions described herein can be prepared according toconventional techniques well known as typified by cake batters andvegetable juices and can be formulated by merely admixing the involvedingredients within the proportions stated in a suitable blender toobtain the desired consistency, homogeneity of dispersion, etc.Alternatively, flavoring compositions in the form of particulate solidscan be conveniently pre pared by admixing the 4-(2,6,6-trimethyl-l ,3-cyclohexadien-l-yl)-2-butanone and/or 4-(6,6-dimethyl-2-methylene-3-cyclohexen-l-yl)-2-butanone with for example gumarabic, gum tragacanth, carrageenan and the like and thereafterspray-drying the resultant mixture whereby to obtain the particularsolid product. Pre-prepared flavor mixes in powder form, e.g., a redcurrant mix or a fruit flavored powder obtained by mixing dried solidcomponents, e.g., starch, sugar and the like and 4-(2,6,6-trimethyl-l,3-cyclohexadien-l-yl)-2-butanone and/or 4-(6,6-dimethyl-Z-methylene-3-cyclohexen-l-yl)-2-butanone in a dry blenderuntil the requisite degree of uniformity is achieved.

It is presently preferred to combine the 4-(2,6,6-trimethyl-l,3-cyclohexadien-l-yl)-2-butanone and/or4-(6,6-dimethyl-Z-methylene-3-cyclohexen-l-yl)-2- butanone with thefollowing adjuvants:

Vunillin Allyl Capt-mite (itral Amyl Butyrate Ethyl Butyratc EthylAcetate Amyl Acetate (innamyl Aldehyde Maltol Acetic Acid Ethyl MethylPhenyl Glycidate Benzyl Acetate Methyl Cinnamate Methyl AnthranilateMethyl Heptinyl Carbonate Methyl Salicylate Beta lonone GammaUndecalactone Diacetyl Anethol 4-( 2,6,6-trimethyl-l ,3-cyclohexadienl-yl)-2- butanone and/or 4(6,6-dimethyl-2-methylene-3-cyclohexen-l-yl)-2-butanone and an auxiliary perfume ingredientincluding, for example, alcohols, aldehydes, nitriles, esters, cyclicesters and natural essential oils may be admixed so that the combinedodors of the individual components produce a pleasant or desiredfragrance. Such perfume compositions usually contain (a) the main noteor the bouquet" or foundation stone of the composition; (11) modifierswhich round off and accompany the main note; fixatives which includeodorous substances which lend a particular note to the perfumethroughout all stages of evaporation and substances which retardevaporation; and (d) topnotes which are usually low boiling freshsmelling materials.

In perfume compositions, the individual component will contribute inparticular olfactory characteristics but the over-all effect of theperfume composition will be the sum of the effects of each of theingredients. Thus, 4-(2,6,6-trimethyl-l,3-cyclohexadien-l-yl)-2-butanone and/or 4-(6,6-dimethyl-2-methylene-3-cyclohexen-l-yl)-2-butanone can be used to alter the aromacharacteristics of a perfume composition, for example, by utilizing ormoderating the olfactory reaction contributed by another ingredient inthe composition.

The amount of the 4-(2,6,6-trimethyl-l ,3-cyclohexadien-l-yl)-2-butanone and/or 4-(6,6-dimethyl2-methylene-3-cyclohexen-l-yl)-2-butanone of our invention whichwill be effective in perfume compositions depend on many factorsincluding the other ingredients, their amounts and the effects which aredesired. It has been found that perfume compositions containing aslittle as 0.05% of 4-(2,6,6-trimethyll,3-cyclohexadien-l-yl)-2-butanoneand/or 4-(6,6- dimethyl-2-methylene-3-cyclohexen-l-yl)-2-butanone oreven less can be used to impart a mimosa type scent odor to soaps,cosmetics and other products. The amount employed can range up to 5% ofthe fragrance components and will depend on considerations of cost,nature of the end product, the effect desired on the finished productand the particular fragrance sought.

4-(2,6,6-trimethyl-l ,3-cyclohexadien-l-yl)-2- butanone and/or4-(6,6-dimethyl-2-methylene-3- cyclohexen-1-yl)-2-butanone are useful inperfume compositions as olfactory components in detergents and soaps;space odorants and deodorants; perfumes; colognes; toilet water; bathpreparations such as bath oils and bath solids; hair preparations suchas lacquers, brilliantines, pomades and shampoo; cosmetic preparationssuch as creams, deodorants, hand lotions and sunscreens; powders such astalcs, dusting powders, face powders and the like. When used as anolfactory component of a perfumed article as little as parts per millionof the 4-(2,6,6-trimethyl-l,3-cyclohexadien-lyl)-2-butanone and/or4-(6,o-dimethyl-Z-methylene-3- cyclohexen-1-yl)-2-butanone will sufficeto impart a low keyed mimosa character which is one of the key odorcharacteristics of mimosa perfume formula tions. Generally, no more than0.5% of 4-(2,6,6- trimethyl-l,3-cyclohexadien-l-yl)-2-butanone and/or4-(6,6-dimethyl-2-methylene-3-cyclohexen-l-yl)-2- butanone based on theultimate end product is required in the perfume composition.

In addition, the perfume composition or fragrance composition of thisinvention contain a vehicle or carrier for the 4-(2,6,6-trimethyl-l,3-cyclohexadienl-yl)- Z-butanone and/or 4-(6,6-dimethyl-2-methylene-3-cyclohexen-l-yl)-2-butanone. The vehicle can be a liquid such as analcohol, a non-toxic alcohol, a non-toxic glycol or the like, Thecarrier can also be an absorbent solid such as a gum (e.g., gum arabic)or components for encapsulating the composition (such as gelatine).

It will thus be apparent that 4-(2,6,6-trimethyl-l,3-cyclohexadien-l-yl)-2-butanone and/or 4-(6,6-dimethyl-2-methylene-3-cyclohexen-l-yl-2-butanone can be utilized toalter the sensory properties, particularly organoleptic properties suchas flavor and/or fragrances of a wide variety of consumable materials.

The following examples are given to illustrate embodiments of theinvention as it is presently preffered to practice it. It will beunderstood that these examples are illustrative and the invention is notto be considered as restricted thereto except as indicated in theappended claims.

EXAMPLE I PERFUME FORMULATION The following mixture is prepared:

butanone imparts to this formulation a low keyed mimosa character whichis one of the key odor characteristics of this type of aroma.

EXAMPLE II PREPARATION OF SOAP COMPOSITION One hundred grams of soapchips are mixed with 1 gram of the perfume composition of Example Iuntil a substantially homogeneous composition is obtained. The perfumedsoap composition exhibits a mimosa characteristic.

EXAMPLE III PREPARATION OF A DETERGENT COMPOSITION A total of 100 gramsof a detergent powder is mixed with 0.15 grams of the perfumecomposition of Example I until a substantially homogeneous compositionis prepared. This composition exhibits a mimosa fragrance.

EXAMPLE IV PREPARATION OF A COSMETIC POWDER COMPOSITION A cosmeticpowder is prepared by mixing in a ball mill 100 grams of talcum powderwith 0.25 grams of 4-(2,6,6-trimethyl-l,3-cyclohexadien-l-yl)-2-butanone. It has an excellentmimosa aroma.

EXAMPLE V PERFUMED LIQUID DETERGENT Concentrated liquid detergent with arich mimosa character are obtained containing 0.10%, 0.15%, and 0.20% of4-( 2,6,6-trimethyl- 1 ,3-cyclohexadienl -yl)-2- butanone. They areprepared by adding and homogeneously mixing the appropriate quantity of4-(2,6,6- trimethyl-l,3-cyclohexadien-l-yl)-2-butanone in the liquiddetergent. The detergents all possess a mimosa fragrance, the intensityincreasing with greater concentrations of4-(2,6,6-trimethyl-l,3-cyclohexadien-l-yl)- Z-butanone.

EXAMPLE VI COLOGNE 4-(2,6,6-trimethyl- 1 ,3-cyclohexadienl -yl )-2-butanone is incorporated in a cologne at a concentration of 2.5% inaqueous ethanol; and into a handkerchief perfume at a concentration of5% (in aqueous ethanol). A distinct and definite mimosa fragrance isimparted to the cologne and to the handkerchief perfume.

EXAMPLE VII The composition of Example I is incorporated in a cologne ata concentration of 2.5% in 85% aqueous ethanol; and into a handkerchiefperfume at a concentration of 20% (in 95% aqueous ethanol). Thecomposition of Example I affords a distinct and definite strong mimosafragrance to that handkerchief perfume and cologne.

EXAMPLE VIII FLAVOR FORMULATIONS The following mixture is prepared:

Ingredients Parts by Weight Vanillin 20 Allyl Caproate l0 Citral 20 AmylButyrate 35 Orange Oil 45 Ethyl Butyrate 75 Ethyl Acetate I85 AmylAcetate I85 Lemon Oil 4004-(2,6,6-trimethyl-l,3-cyclohexadien-l-yl)-2-butanone was added to 975grams of the above mixture which was then called Test Composition. Acontrol composition was prepared by adding 25 grams of additional lemonoil to 975 grams of the above mixture.

The test and control compositions were added to the food productsdescribed hereinafter and the proportions shown for kilograms ofmaterial to be flavored:

Cake 20 grams Pudding 5-10 grams Cooked sugar 15-20 grams Cooked sugar100 ml of sugar syrup (prepared by dissolving l kilogram of sucrose in600 ml of water) and 20 grams of glucrose were mixed together and slowlyheated to l45 C. The flavor was added and the mass allowed to cool andharden.

Pudding To 500 ml ofwarmed milk were added wth stirring a mixture of 60grams sucrose and 3 grams of pectin. The mixture was boiled for a fewseconds and the flavor was added. The mixture was allowed to cool.

Cake The following ingredients were mixed together:

100 grams vegetable margarin 1.5 grams sodium chloride I00 grams sucrose2 eggs 100 grams flour The flavor was added and the mass was cooked for40 minutes at C. The finished foodstuff samples were tested by a panelof trained persons who had to express their vies about the flavor of thesamples. All members of the panel declared with no hesitation that thetest samples had a more distinguished fruity and woody note than thecontrol samples and at the same time a red-berry character.

EXAMPLE IX STRAWBERRY FLAVOR FORMULATION The following mixture isprepared: 10

Parts Ingredients by Weight Maltol Glacial Acetic acid Ethyl MethylPhenyl Glycidate Benzyl Acetate Vanillin Methyl Cinnamte MethylAnthranilate Methyl Heptinyl Carbonate Methyl SaIieylate Beta IononeGamma Undecalaetone Diaeetyl Anethol Ethyl Alcohol (95% aqueous)4-(2,6.6-trimethyl-I,3-cyclohexadien-l-yI)-2- butanone The4-(2,6,6-trimethyI-l,3-cyclohexadien-I-yl)-2- butanone imparts to theabove strawberry formulation 21 berry, seedy and woody group of notesthereby making the formulation much more natural-like.

EXAMPLE X STRAWBERRY FLAVOR FORMULATION The following mixture isprepared:

Parts Ingredients by Weight Maltol Glacial Acetic Acid Ethyl MethylPhenyl Glycidate Benzyl Acetate Vanillin Methyl Cinnamate MethylAnthranilate Methyl Heptinyl Carbonate Methyl Salicylate Beta IononeGamma Undecalactone Diacetyl Anethol Ethyl Alcohol (957r aqueous)4-(6.o-dimethyl-2-methyIene-3-cyclohexenl-yl)2-butanone The4-(6,6-dimethyl-Z-methylene-3-cyclohexen-1- yl)-2-butanone imparts tothe above strawberry formulation a berry, seedy and woody group of notesthereby making the formulation much more natural-like.

EXAMPLE XI STRAWBERRY FLAVOR FORMULATION The following mixture isprepared:

Ingredients Maltol Glacial Acetic Acid Ethyl Methyl Phenyl GlycidateBenzyl Acetate Vanillin Methyl Cinnamate Methyl Anthranilate MethylHeptinyl Carbonate by Weight -Continued Parts Ingredients by WeightMethyl Salicylate 0.2 Beta lonone 0.2 Gamma Undecalaetone 0.2 Diacetyl0.2 Anethol 0.07 Ethyl Alcohol (95% aqueous) 89.5] 90:10 weighuweightmixture of 4-(2,6,6-trimethyl-I.3-cyclohexadienl-yl)-2-hulanone and 4-(6,6-dimethyl-Z-methylene-lI-eyclohexen- I -yl )-Zhutanone The4-(2,6,6-trimethyI-1,3-cyclohexadien-I-yl)-2- butanone and4-(6,6-dimethyl-2-methylene-3- cyc1ohexen--yl)-2-butanone imparts to theabove strawberry formulation a berry, seedy and woody group of notesthereby making the formulation much more natural-like.

EXAMPLE'X'II The following mixture is prepared:

Ingredients Parts by Weight Natural Raspberry Concentrate Juice 2 V27:

Water Sugar syrup (37 V2 Baume') 12 /27? The seedy note of thisraspberry juice is imparted in increasing strength by addition of eitherof the following materials at the rate of from 0.02 ppm up to 1.0 ppm:

4-(2,6,6-trimethyl-l ,3-cyclohexadienl -yl )-2- butanone4-(6,6-dimethyl-2-methyIcne-3- cyclohexen-l-yl)-2-butanone zl0weightweight mixture of4-(2.(i.6-tri1nethyll,3-eyclohexadien-l-yl)-2-butanone and 4-(6,6-dimethyl-Z-methylene-3-cyclohexen-l-yl)-2- butanone EXAMPLE XIII PERFUMEFORMULATION The following mixture is prepared:

butanone The 4-(2,6,6-trimethyl-l,3-cyclohexadien-I-yl)-2- butanoneimparts to the above floral type formulation, a sweet, raspberry,"mimosa" note.

11 EXAMPLE XIV PERFUME FORMULATION The following mixture is prepared:

The 4-(6,6-dimethyl-2-methylene-3-cyc1ohexen-l-yl- Z-butanone imparts tothe above floral type formulation, a sweet, raspberry, mimosa note.

EXAMPLE XV PERFUME FORMULATION The following mixture is prepared:

Ingredients Indol 2.( Methyl Anthranilate 2.0 n-Heptyl Cyelopentanonc3.0 Grisalva (produced by the 5071 sulfuric acid 40 treatment of3-ethy1-l-(2.2.6-trimethylcyclohexen-S-yl-l )-hexen-3-ol-6) 6.7-Dihydrol,1 .2,3,3*pcnttlmethyI-4-(5H) indanone 2.0

(produced according to the preparation of A of Swiss Patent 523,962) Oilof Bitter Orange 5.0 2-Oxa-1.l,3.3-tetramethyl-2,3.5,6,7.8-hexahydro 5.0

lH-benzene-(f) indene Terpineol Coeur 10.0 Nerolidol 10.0Z-t-butyl-cyclohexanyl acetate 20.0 Linalyl Acetate 90.0 Linalool 1 10.04 (4-methy1-4-hydroxyamyl)-A -cyclohexene- 20.0

carboxaldehyde Benzyl Alcohol 90.0 Benzyl Agetate 150.0

Ingredients Parts by Weight a-Dihydro lonone having the structure: 9.6grams Quinoline 3.2 grams Chloroform 25 ml Ingredients Parts by WeightIndol 2.0 Methyl Anthranilate 2.0 n-Heptyl Cyclopentanone 3.0 Grisalva(produced by the 50% sulfuric acid 4.0

treatment of 3-ethyl-l-(2.2,6-trimethylcyclohexenfi-yld )-hexene-3-ol6)6.7-Dihydro-l,1.2.3.3-pentamcthyl-4-(SH) indanone 2.0

(produced according to the preparation of A of Swiss PatentlH-ben7.-(f)-indene Oil of Bitter Orange 5.0Z-Oxa-Ll.3.3-tetramethyl-2.3.5,6.7,8-hexahydro- 5.0

lH-ben7.-( 5 )-indene Terpincol Coeur 10.0 Nerolidol 10.0Z-bbutyl-cyclohexanyl acetate 20.0 Linalyl Acetate 90.0 Linalool 110.0 4(4-mctl1yl-4-hydroxyamyl)-A cyclohexenc- 20.0

carboxaldehydc Benzyl Alcohol 90.0 Benzyl Acetate 150.04-(6,6-dimethyl-2-methylenc-3-cyclohexen-1-y1)- 3.0

Z-butanone 2S The resulting mixture is cooled in an ice-sodium chloridebath and a mixture of 3.2 grams of bromine and 9 ml chloroform is addeddrop-wise with stirring over a half hour period. The reaction mass isthen stirred at 5 C for a period of 5 hours and then concentrated underreduced pressure. The resulting residue is then heated on a steam bathfor a period of 3 hours Parts by Weight 90:10 Tveightzweight mixture4-(2 ,o, 6-trimet hyll B-cy cIoIiexadien T-yli ibutanoh and 146.6

dimethyl-2-methylene-3-cyc1ohexen-1-yl)-2-butanone EXAMPLE XVIPREPARATION OF MIXTURE OF 4-(2,6.6-TRIMETHYL-l,3-CYCLOI-IEXADIEN-1-YL)-2-BUTANONE AND 4-(6.6-DIMETHYL-2-METHYLENE-3-CYCLOHEXEN-1-YL)-2-BUTANONE Into a ml three-neck flask equipped withreflux condenser, thermometer, magnetic stirrer. addition funnel andnitrogen purge, the following materials are added:

after 11 ml ofN N-Diethylaniline has been added to the residue. After 3hours 2.5 ml pyridine is then added to the reaction mass and heating iscontinued for a half hour longer. To the cooled reaction mixture areadded 50 ml of 5 N Hydrochloric acid. The aqueous layer is thenextracted with three 100 ml portions of n-pentane. The combined pentaneextracts are washed with two 50 ml portions of 5 N hydrochloric acid,then two 50 ml 10% sodium bicarbonate solution portions and two 100 mlportions of distilled water. The pentane extracts are then evaporatedafter drying over anhydrous sodium sulfate yielding confirmed byinfrared and mass spectral analysis) a mixture containing 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-y1)-2-butanone and 10%4-(6,6-dimethyl-Z-methylene-3-cyc1ohexen-1-y1)- 2-butanone (over-allyield: 8.8%). The 90:10 mixture of I4-(2,6,6-trimethyl-1,3-cyclohexadien-l-yl)-2- butanone and4-(6,6-dimethyl-2methylene-3- cyclohexen-l-yl)-2-butanone distills at 65C and at mm Hg. pressure.

What is claimed is:

1. A process for altering the fragrance of a consumable materialselected from the froup consisting of a soap, detergent cosmetic, spacedeodorant, space odorant, and perfume composition which comprises adding

1. A PROCESS FOR ALTERING THE FRAGANCE OF A CONSUMABLE MATERIAL SELECTEDFROM THE FROUP CONSISTING OF A SOAP, DETERGENT COSMETIC, SPACEDEODORANT, SPACE ODORANT, AND PERFUME COMPOSITION WHICH COMPRISES ADDINGTHERETO A SMALL BUT EFFECTIVE AMOUNT OF A BUTANONE COMPOUND SELECTEDFROM THE GROUP CONSISTING OF4-(2,6,6-TRIMETHYL-1,3-CYCLOHEXADIEN-I-YL)-2BUTANONE AND4-(6,6-DIMETHYL-2-METHYLENE-3-CYCLOHEXEN-1YL)-2-BUTANONE.
 2. The processof claim 1 wherein the butanone compound is 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanone.